Page 11 of 17
The Journal of Organic Chemistry
7.33–6.27 (m, 10H), 6.60 (d, J = 15.6 Hz, 1H), 6.31 (dd, J =
16.0, 8.0 Hz, 1H), 4.91 (d, J = 8.0 Hz, 1H), 3.62–3.55 (m, 1H),
3.52–3.44 (m, 1H), 1.26 (t, J = 7.2 Hz, 3H).
tmajor = 16.1 min, tminor = 22.6 min. 1H NMR (400 MHz,
CDCl3): δ 7.43–7.21 (m, 11H), 6.99–6.64 (m, 2H), 6.62 (d, J =
16.0 Hz, 1H), 6.33 (dd, J = 16.0, 7.2 Hz, 1H), 5.05 (d, J = 7.2
Hz, 1H), 4.70 (s, 2H).
2-(((S,E)-1,3-Diphenylallyloxy)methyl)pyridine (Table 1,
entry 11): Colorless oil (70% yield, 64% ee), Rf = 0.16 (5:1
hexanes/AcOEt). HPLC (Daicel OD-H column, n-hexane:i-
1
2
3
4
5
6
7
8
Butyl (S,E)-1,3-diphenylallyl ether (Table 1, entry 3):
Colorless oil (82% yield, 97% ee), Rf = 0.21 (50:1
hexanes/AcOEt). HPLC (Daicel OJ-H column, n-hexane:i-
PrOH = 99.5:0.5, Flow rate = 1.0 mL/min, λ = 254 nm): tminor
1
= 10.2 min, tmajor = 11.4 min. H NMR (400 MHz, CDCl3): δ
PrOH = 85:15, Flow rate = 0.5 mL/min, λ = 254 nm): tmajor =
1
7.40–7.33 (m, 6H), 7.40–7.33 (m, 8H), 7.30–7.25 (m, 3H),
7.23–7.19 (m, 1H), 6.60 (d, J = 16.0 Hz, 1H), 6.29 (dd, J =
16.0, 6.8 Hz, 1H), 4.89 (d, J = 6.8 Hz, 1H), 3.55–3.50 (m, 1H),
3.44–3.39 (m, 1H), 1.66–1.59 (m, 2H), 1.46–1.36 (m, 2H),
0.91 (t, J = 7.2 Hz, 3H).
11.5 min, tminor = 14.1 min. H NMR (600 MHz, CDCl3): δ
8.53 (d, J = 4.8 Hz, 1H), 7.69 (t, J = 7.8 Hz, 1H), 7.55 (d, J =
7.8 Hz, 1H), 7.45 (d, J = 7.8 Hz, 2H), 7.37 (t, J = 8.4 Hz, 4H),
7.31–7.28 (m, 3H), 7.22 (t, J = 6.6 Hz, 1H), 7.17 (t, J = 4.8
Hz, 1H), 6.68 (d, J = 16.0 Hz, 1H), 6.35 (dd, J = 16.0, 6.6 Hz,
1H), 5.09 (d, J = 6.6 Hz, 1H), 4.74 (d, J = 13.8 Hz, 1H), 4.67
(d, J = 13.8 Hz, 1H).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Allyl (S,E)-1,3-diphenylallyl ether (Table 1, entry 4):
Colorless oil (81% yield, 82% ee), Rf
= 0.5 (10:1
hexanes/AcOEt). HPLC (Daicel OD-H column, n-hexane:i-
PrOH = 97.5:2.5, Flow rate = 0.25 mL/min, λ = 254 nm): tmajor
2-(((S,E)-1,3-Diphenylallyloxy)methyl)tetrahydrofuran
(Table 1, entry 12): Colorless oil (60% yield, 93% ee), Rf =
0.39 (5:1 hexanes/AcOEt). HPLC (Daicel AD-H column, n-
hexane:i-PrOH = 99:1, Flow rate = 0.5 mL/min, λ = 254 nm):
tmajor = 14.0, 16.8 min (two (S,E)-isomers), tminor = 15.2, 16.1
min (two (R,E)-isomers). 1H NMR (400 MHz, CDCl3): δ 7.40–
7.26 (m, 20H), 6.63 (d, J = 16.0 Hz, 1H), 6.59 (d, J = 16.0 Hz,
1H), 6.33 (dd, J = 16.0, 7.2 Hz, 1H), 6.29 (dd, J =16.0, 7.2 Hz,
1H), 4.98 (d, J = 7.2 Hz, 2H), 4.15–4.10 (m, 2H), 3.92–3.86
(m, 2H), 3.78 (q, J = 8 Hz, 2H), 3.58–3.52 (m, 2H), 3.49–3.42
(m, 2H), 2.00–1.85 (m, 6H), 1.71–1.62 (m, 2H).
1
= 36.8 min, tminor = 39.5 min. H NMR (600 MHz, CDCl3): δ
7.53–7.23 (m, 10H), 6.61 (d, J = 15.6 Hz, 1H), 6.30 (dd, J =
15.6, 6.8 Hz, 1H), 5.99–5.95 (m, 1H), 5.31 (d, J = 17.4 Hz,
1H), 5.21 (d, J = 11.4 Hz, 1H), 4.98 (d, J = 6.8 Hz, 1H), 4.07–
4.03 (m, 2H).
(S,E)-1,3-Diphenylallyl 3-methyl-2-butenyl ether (Table
1, entry 5): Colorless oil (60% yield, 69% ee), Rf = 0.29 (50:1
hexanes/AcOEt). HPLC (Daicel OD-H column, n-hexane:i-
PrOH = 99:1, Flow rate = 0.2 mL/min, λ = 254 nm): tmajor
=
1
9.2 min, tminor = 10.2 min. H NMR (400 MHz, CDCl3): δ
7.30–6.29 (m, 10H), 6.58 (d, J = 16.0 Hz, 1H), 6.32 (dd, J =
16.0, 7.2 Hz, 1H), 5.41 (t, J = 6.8 Hz, 1H), 4.95 (d, J = 7.2 Hz,
1H), 1.75 (s, 3H), 1.61 (s, 3H).
2-((S,E)-1,3-Diphenylallyloxy)-2,3-dihydro-1H-indene
(Table 1, entry 13): Colorless oil (60% yield, 91% ee), Rf =
0.16 (5:1 hexanes/AcOEt). HPLC (Daicel OD-H column, n-
hexane:i-PrOH = 98.5:1.5, Flow rate = 0.5 mL/min, λ = 254
1
Benzyl (S,E)-1,3-diphenylallyl ether (Table 1, entry 6):
Colorless oil (83% yield, 80% ee), Rf = 0.26 (50:1
hexanes/AcOEt). HPLC (Daicel OD-H column, n-hexane:i-
PrOH = 98.5:1.5, Flow rate = 0.3 mL/min, λ = 254 nm): tmajor
nm): tmajor = 38.6 min, tminor = 41.3 min. H NMR (600 MHz,
CDCl3): δ 7.41–7.24 (m, 14H), 6.61 (d, J = 15.6 Hz, 1H), 6.32
(dd, J = 15.6, 7.2 Hz, 1H), 5.08 (d, J = 7.2 Hz, 1H), 4.51 (m,
1H), 3.22–3.02 (m, 4H).
1
= 18.7 min, tminor = 20.9 min. H NMR (400 MHz, CDCl3): δ
(S,E)-1,3-Di(o-tolyl)allyl methyl ether (Table 2, entry 1):
Colorless oil (99% yield, 85% ee), Rf = 0.29 (50:1
7.44–7.20 (m, 15H), 6.62 (d, J = 16.0 Hz, 1H), 6.33 (dd, J =
16.0, 7.2 Hz, 1H), 5.00 (d, J = 7.2 Hz, 1H), 4.57 (s, 2H).
(S,E)-1,3-Diphenylallyl 2-phenethyl ether (Table 1, entry
7): Colorless oil (85% yield, 72% ee), Rf = 0.16 (20:1
hexanes/AcOEt). HPLC (Daicel OJ-H column, n-hexane:i-
20
hexanes/AcOEt); [α]D −3.0 (c 1.00, CHCl3). HPLC (Daicel
AD-H column, n-hexane:i-PrOH = 99.7:0.3, Flow rate = 0.3
1
mL/min, λ = 254 nm): tmajor = 23.7 min, tminor = 26.6 min. H
NMR (400 MHz, CDCl3): δ 7.48–7.46 (m, 1H), 7.42–7.40 (m,
1H), 7.25–7.12 (m, 6H), 6.80 (d, J = 16.0 Hz, 1H), 6.11 (dd, J
= 16.0, 6.8 Hz, 1H), 4.99 (d, J = 6.8 Hz, 1H), 3.39 (s, 3H),
2.38 (s, 3H), 2.33 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
δ 139.0, 135.8, 135.6, 135.5, 130.5, 130.4, 130.2, 129.5, 127.6,
127.5, 126.4, 126.3, 126.1, 125.9, 81.5, 56.4, 19.8, 19.3; IR
(film): vmax 3065, 3020, 2953, 2926, 2853, 2818, 1489, 1458,
1188, 1091, 1049, 966, 750, 727, 575 cm−1; HRMS (ESI-TOF)
m/z: [M − (OCH3)]+ Calcd for C17H17 221.1330; Found
221.1323.
PrOH = 99:1, Flow rate = 1.0 mL/min, λ = 254 nm): tminor
=
1
28.3 min, tmajor = 31.6 min. H NMR (400 MHz, CDCl3): δ
7.26–7.21 (m, 15H), 6.57 (d, J = 16.0 Hz, 1H), 6.25 (dd, J =
16.0, 7.2 Hz, 1H), 4.91 (d, J = 7.2 Hz, 1H), 3.78–3.72 (m, 1H),
3.67–3.61 (m, 1H), 2.96 (t, J = 6.8 Hz, 2H).
Cinnamyl (S,E)-1,3-diphenylallyl ether (Table 1, entry
8): Colorless oil (87% yield, 78% ee), Rf = 0.18 (10:1
hexanes/AcOEt). HPLC (Daicel OJ-H column, n-hexane:i-
PrOH = 70:30, Flow rate = 1.0 mL/min, λ = 254 nm): tmajor
=
1
14.3 min, tminor = 16.9 min. H NMR (400 MHz, CDCl3): δ
7.40–7.26 (m, 15H), 6.66–6.31 (m, 2H), 6.37–6.31 (m, 2H),
5.05 (d, J = 6.8 Hz, 1H), 4.22–4.20 (m, 2H).
(S,E)-1,3-Di(m-tolyl)allyl methyl ether (Table 2, entry
2): Colorless oil (99% yield, 97% ee), Rf = 0.29 (50:1
20
hexanes/AcOEt); [α]D −6.7 (c 0.99, CHCl3); HPLC (Daicel
2-(((S,E)-1,3-Diphenylallyloxy)methyl)furan (Table 1,
entry 9): Colorless oil (84% yield, 92% ee), Rf = 0.32 (50:1
hexanes/AcOEt). HPLC (Daicel OD-H column, n-hexane:i-
OJ-H column, n-hexane:i-PrOH = 99.5:0.5, Flow rate = 1.0
1
mL/min, λ = 254 nm): tminor = 23.4 min, tmajor = 26.6 min. H
NMR (400 MHz, CDCl3): δ 7.26–7.17 (m, 6H), 7.10–7.08 (m,
1H), 7.04–7.03 (m, 1H), 6.59 (d, J = 16.0 Hz, 1H), 6.25 (dd, J
= 16.0, 6.8 Hz, 1H), 4.74 (d, J = 6.8 Hz, 1H), 3.37 (s, 3H),
2.35 (s, 3H), 2.31 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
δ 141.0, 138.2, 138.0, 136.6, 131.5, 130.0, 128.5, 128.4, 127.4,
127.3, 123.9, 123.8, 84.4, 56.4, 21.5, 21.3; IR (film): vmax
3026, 2922, 2818, 1604, 1489, 1089, 964, 781, 704, 692 cm−1;
HRMS (ESI-TOF) m/z: [M − (OCH3)]+ Calcd for C17H17
221.1330; Found 221.1325.
PrOH = 90:10, Flow rate = 1.0 mL/min, λ = 254 nm): tmajor
=
1
11.1 min, tminor = 15.1 min. H NMR (600 MHz, CDCl3): δ
7.41–7.24 (m, 11H), 6.60 (d, J = 16.0 Hz, 1H), 6.33–6.29 (m,
3H), 5.02 (d, J = 6.8 Hz, 1H), 4.51 (s, 1H), 4.49 (s, 1H).
2-(((S,E)-1,3-Diphenylallyloxy)methyl)thiophene (Table
1, entry 10): Colorless oil (80% yield, 72% ee), Rf = 0.15
(20:1 hexanes/AcOEt). HPLC (Daicel OJ-H column, n-
hexane:i-PrOH = 95:5, Flow rate = 1.0 mL/min, λ = 254 nm):
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